Anthropogenic inputs of boron into urban atmosphere: Evidence from boron isotopes of precipitations in Guiyang City,China

Boron (B) concentrations and isotopic compositions were measured in the precipitations of Guiyang, China for one year. Most precipitation samples have boron concentrations of from 2.1 to 4.8 ng ml^?1, and δ¹¹B values of from +2.0‰ to +30.0‰. Boron concentrations and δ¹¹B values of heavy rain samples are generally higher than those of light rain and snow samples. Anthropogenic inputs provided most of the SO₄^2? and NO₃^?, which were predominant ions in the precipitation. The major cation Ca²⁺ in the precipitation was mainly originated from local dust.The total boron in precipitation from Guiyang is explained by the mixing model of three boron sources. Assuming a δ¹¹B value of +45‰ for the seawater component, contributions of marine source, organic matter and biomass combustion, and coal combustion were estimated to be 32%, 49%, and 19%, respectively to the total boron in Guiyang precipitations. The coal combustion and biomass (and/or organic matter) combustion showed different contributions of boron to the rainwaters in different seasons, the former in cold season while the latter in summer season had a more marked influence on the chemical and isotopic composition of the rainwater. The largest contribution of seawater-originated boron was observed for the heavy rain samples, which was up to 68%. This study indicates that the atmospheric environment of Guiyang city was strongly influenced by human activities, and boron isotopic composition is of great sensitivity to anthropogenic sources and can be a powerful technique to trace various sources of atmospheric emissions and even their origins.     

Using variances in hydrocarbon concentration and carbon stable isotope to determine the important influence of irrigated water on petroleum accumulation in surface soil

Hunpu is a wastewater-irrigated area southwest of Shenyang. To evaluate petroleum contamination and identify its sources at the area, the aliphatic hydrocarbons and compound-specific carbon stable isotopes of n-alkanes in the soil, irrigation water, and atmospheric deposition were analyzed. The analyses of hydrocarbon concentrations and geochemical characteristics reveal that the water is moderately contaminated by degraded heavy oil. According to the isotope analysis, inputs of modern C3 plants and degraded petroleum are present in the water, air, and soil. The similarities and dissimilarities among the water, air, and soil samples were determined by concentration, isotope, and multivariate statistical analyses. Hydrocarbons from various sources, as well as the water/atmospheric deposition samples, are more effectively differentiated through principal component analysis of carbon stable isotope ratios (δ¹³C) relative to hydrocarbon concentrations. Redundancy analysis indicates that 57.1 % of the variance in the δ¹³C of the soil can be explained by the δ¹³C of both the water and air, and 35.5 % of the variance in the hydrocarbon concentrations of the soil can be explained by hydrocarbon concentrations of both the water and the air. The δ¹³C in the atmospheric deposition accounts for 28.2 % of the δ¹³C variance in the soil, which is considerably higher than the variance in hydrocarbon concentrations of the soil explained by hydrocarbon concentrations of the atmospheric deposition (7.7 %). In contrast to δ¹³C analysis, the analysis of hydrocarbon concentrations underestimates the effect of petroleum contamination in the irrigated water and air on the surface soil. Overall, the irrigated water exerts a larger effect on the surface soil than does the atmospheric deposition.     

Organic and inorganic components of aerosols over the central Himalayas: winter and summer variations in stable carbon and nitrogen isotopic composition

The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ¹³C and δ¹⁵N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. ?24.0?‰), mostly originated from biomass burning of C₄ plants. On the contrary, the aerosols in summer showed smaller δ¹³C values (?26.0?‰), indicating that they are originated from vascular plants (mostly of C₃ plants). The secondary ions (i.e., SO₄ ^2?, NH₄ ⁺, and NO₃ ^?) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.     

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

The chemical composition of marine aerosols as a function of their size is an important parameter for the evaluation of their impact on the global climate system. In this work we model fine particle organic matter emitted by sea spray processes and its influence on the aerosol chemical properties at the global scale using the off-line global Chemistry-Transport Model TM5. TM5 is coupled to a microphysical aerosol dynamics model providing size resolved information on particle masses and numbers. The mass of the emitted sea spray particles is partitioned between water insoluble organic matter (WIOM) and sea salt components in the accumulation mode using a function that relates the emitted organic fraction to the surface ocean chlorophyll-a concentrations. The global emission in the sub-micron size range of organic matter by sea spray process is 8.2 Tg yr^?1, compared to 24 Tg fine yr^?1 sea-salt emissions. When the marine sources are included, the concentrations of modelled primary particulate organic matter (POM) increase mainly over the oceans. The model predictions of WIOM and sea salt are evaluated against measurements carried out at Mace Head (Northern Hemisphere) and Amsterdam Island (Southern Hemisphere), showing that in clean marine conditions WIOM marine emissions contribute significantly to POM values.     

Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines

Organophosphorus compounds (OPCs) and stable isotope ratios (δ¹³C and δ¹⁵N) were determined in 58 fishes belonging to 20 species collected from Manila Bay, the Philippines. OPCs were detected in most of the samples and found up to μg/g lw (lipid weight) level, suggesting their ubiquitous presence in the coastal marine environment of the Philippines. Higher levels (>1000 ng/g lw) of total OPCs were determined in yellowstriped goatfish, silver sillago, tripletail wrasse and bumpnose trevally indicates either their active uptake from ambient water or lower metabolic capacity of these species. Levels of triphenyl phosphate (TPhP) in demersal species showed a positive correlation with δ¹⁵N, indicating that TPhP was adsorbed onto the particle, settled down to the bottom sediment and accumulated through the benthic food web rather than the pelagic. Estimated dietary intake of OPCs in Manila Bay fishes were four to five orders of magnitude lower than the proposed reference dose (RfD).     

Ecosystem functioning approach applied to a large contaminated coastal site: the study case of the Mar Piccolo of Taranto (Ionian Sea)

Knowledge on ecosystem functioning can largely contribute to promote ecosystem-based management and its application. The Mar Piccolo of Taranto is a densely populated area at a high risk of environmental crisis. Here, planktonic primary production (PP) and heterotrophic prokaryotic production (HPP) were measured as proxies of functioning in three sampling sites located in two inlets at different levels of industrial contamination, during three sampling surveys (June 2013, February and April 2014). To have a better overall view and provide some insights into the benthic-pelagic coupling, we integrated PP and HPP in the water column with those in the sediments and then discussed this with the origin of the organic matter pools based on analysis of stable isotopes. Heavy metals and polychlorobiphenyls (PCBs) were also analysed in the surface (1 cm) sediment layer and related to the overall ecosystem functioning. Multidimensional scaling (MDS) analysis, based on the main data, clearly separated the second inlet from the first one, more severely impacted by anthropogenic activities. The stable isotope mixing model suggested the prevalent terrestrial/riverine origin of the particulate organic matter pools (mean 45.5 %) in all sampling periods, whereas phytoplankton contributed up to 29 % in February. Planktonic PP and HPP rates followed the same pattern over the entire study period and seemed to respond to phytoplankton dynamics confirming this community as the main driver for the C cycling in the water column. On the contrary, benthic PP rates were almost negligible while HPP rates were lower or comparable to those in the water column indicating that although the Mar Piccolo is very shallow, the water column is much more productive than the surface sediments. The sediment resuspension is likely responsible for a pulsed input of contaminants into the water column. However, their interference with the proper functioning of the pelagic ecosystem seems to be limited to the bottom layers.     

The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99?‰ for the δ⁶⁵Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in ⁶⁵Cu compared to the soil. As a result of the same trial, the δ⁵⁶Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal–organic complexation and weathering can modify particular isotopic signatures.     

Chemical signals of epiphytic lichens in southwestern North America; natural versus man-made sources for airborne particulates

Ambient airborne particulate matter (PM) in southwestern North America consists of naturally derived desert dust, plus anthropogenic inputs from several sources. Epiphytic lichens (Usnea sp.) in this region are a useful biomonitor for the airborne PM because they derive nutrients and moisture largely from incorporated atmospheric aerosols, and not by absorption from the host tree limb from which they are suspended. Using a broad-based sampling strategy from southern Chihuahua, Mexico, to northern New Mexico, USA, we show that select elemental abundance ratios and lead isotopes from epiphytic lichens are useful for distinguishing between sources of airborne PM, and for gauging anthropogenic inputs into desert ecosystems. Abundance patterns of the trace elements La, Nd, and Sm in the lichens suggest origination from continental crust, but rare earth elements display a pronounced enrichment relative to the major element Fe by a factor of about 5. This enrichment appears related to geologic weathering, aeolian transport, and grain-size biases toward trace-element-rich mineral grains in the arid setting. Using the metal Pb as an indicator of human inputs, epiphytic lichens typically show Pb enrichments by a factor of about 25–60 over typical upper crustal values. Regional-scale differences in Pb isotope ratios of these lichens relate to different pollutant sources in southwestern North America.     

Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter

Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7–5.1, TNT: 4.8–5.0). After separation of POM, concentrations of ¹⁴C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8–6.0 and 8.5–9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter.     

Contamination assessment of mercury and arsenic in roadway dust from Baoji,China

The physicochemical properties and the contamination levels of mercury and arsenic in roadway dust from Baoji, NW China were investigated using an Atomic Fluorescence Spectrophotometer. Contamination levels were assessed based on the geoaccumulation index and the enrichment factor. The results show that magnetic susceptibilities of roadway dust were higher than Holocene loess–soil of central Shaanxi Loess Plateau. The mean contents of organic matter, PM10 and PM100 were 8.8%, 21.8% and 98.6%, respectively. Mercury concentration ranged from 0.48 to 2.32 μg g^?1, with a mean value of 1.11 μg g^?1, 17.1 times the Chinese soil mercury background value and 37 times the Shaanxi soil mercury background value. Arsenic concentration ranged from 9.0 to 42.8 μg g^?1, with a mean value of 19.8 μg g^?1, 1.8 times the Chinese and Shaanxi soil arsenic background values. The geoaccumlation index and enrichment factor indicate that mercury in the dust mainly originated from anthropogenic sources with ratings of “strongly polluted” and “strongly to extremely polluted”, whereas arsenic in dust originated from both natural and anthropogenic sources, with a ratings of “moderately to strongly polluted” and “strongly polluted”. Industrial activities, such as a coal-fired power station, coke-oven plant, and cement manufacturing plant, augmented by vehicular traffic, are the anthropogenic sources of mercury and arsenic in the roadway dust.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

Sulfur and Carbon Cycling in a Flue Gas Desulfurization Sludge Disposal Site

Abstract

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial δ¹³C 3.2–3.8‰), gypsum (initial δ³⁴S 7.6–8.6‰), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-δ³⁴S sulfide, consuming organic carbon and generating low-δ¹³C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has δ³⁴S near 6‰, and calcite has δ¹³C as low as -1.7‰; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.     

Reconstructing historical trends of polycyclic aromatic hydrocarbon deposition in a remote area of Spain using herbarium moss material

Herbarium mosses from 1879–1881, 1973–1975 and 2006–2007 were used to investigate the historical changes of atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) at a remote site in Northern Spain. Natural abundance of nitrogen and carbon isotopes was also measured in order to assess the evolution of emissions from anthropogenic sources. Nitrogen and PAH concentrations as well as δ¹³C and δ¹⁵N ratios were significantly higher in 19th century samples compared to present century samples. Moreover, PAH distribution varied over the centuries, with the trend towards enrichment in light PAHs. The carbon, nitrogen and PAH concentrations measured in the mosses tally with the historical evolution of anthropogenic emissions in the area, mainly influenced by changes in economic activities, domestic heating and road traffic density. Mosses provided by herbaria seem to offer the possibility of studying long-term temporal evolution of atmospheric PAH deposition.     

Microbenthic community structure and trophic status of sediments in the Mar Piccolo of Taranto (Mediterranean,Ionian Sea)

This study aimed to assess the benthic ecosystem trophic status in a heavily polluted marine area and the response of the microbenthic community to multiple and diffuse anthropogenic impacts, integrating information coming from the active and resting (plankton’s cysts) components of microbenthos. Two sampling campaigns were carried out in the period 2013–2014 and four sampling sites at different levels of industrial contamination were chosen within the first and second inlet of the Mar Piccolo of Taranto. The chemical contamination affected to a higher extent the active microbenthos than the resting one. In the central part of the first inlet, characterised by more marine features, thrives a very rich and biodiverse microbenthic community. In contrast, at the polluted site near the military navy arsenal, extremely low densities (9576?±?1732 cells cm^?3) were observed for active microbenthos, but not for the resting community. Here, the high level of contamination selected for tychopelagic diatom species, i.e., thriving just above the surface sediments, while the other life forms died or moved away. Following the adoption of a 10 μm mesh, for the first time, resting spores produced by small diatoms of the genus Chaetoceros were found. Our results further indicate that although the Mar Piccolo is very shallow, the benthic system is scarcely productive, likely as a consequence of the accumulated contaminants in the surface sediments that probably interfere with the proper functioning of the benthic ecosystem.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ¹³C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

Influence of algal organic matter on metal accumulation in adjacent sediments of aquaculture from a tropical coast region

The rapid development of coastal aquaculture in recent decades has led to excessive discharge of organic matter and nutrients into surrounding waters, which could result in eutrophication and potentially affect metal cycling. In our study, the influence of algal organic matter on metal accumulation was examined in three coastal sediment cores taken from a tropical region, Hainan Island, China. Overall, metal pollution adjacent to aquaculture ponds remained at low levels on the coast, except Zn, Cd, and Sn were moderately to highly enriched in the Dongjiao sediments. The δ¹³C values and the atomic C/N ratios indicated a major contribution of phytoplankton to sedimentary organic matter at the Dongjiao site. Moreover, both the algae-derived organic matter and effluent nitrogen were significantly associated with the enriched Zn, Cd, and Sn, suggesting that nutrient-induced phytoplankton growth and its organic matter may act as a “biological pump” to enhance the accumulation of metals. Wastewater treatment for aquaculture ponds should include the control of algal organic matter.

     

Urban-Center CO Air Quality Projections

The distribution of mutagenic activity and nitroaromatic components of polycyclic organic matter (POM) in ambient air at industrial, urban, suburban, rural, and remote sites was studied using organic extracts from high volume aerosol samples. Direct-acting mutagens including 1-nitropyrene (1-NP), dinitropyrenes (DNP), and hydroxynitropyrenes (HNP) were measured by high performance liquid chromatography while the mutagenicity was determined in the Salmonella bioassay with strain TA-98. Benzo(a)pyrene (BaP), one of the possible precursors of nitroaromatic compounds in POM, was also measured. In comparing samples from a range of sites, TSP and the concentration of BaP per mass of particulate matter decreased, as expected, at greater distances from urban and industrial combustion sources. However, the concentrations of polar nitroaromatic POM compounds per mass of particles were higher at a remote site than in nonindustrial urban and suburban areas. The mutagenicity in particulate matter extracts from the remote area was predominantly (>90 percent) in the very polar fractions. There were also high atmospheric levels of nitroaromatic compounds and mutagenicity in heavily industrialized areas. These observations may reflect the influences of source emissions, atmospheric transformations of POM compounds, and ther atmospheric processes on the composition of ambient suspended particulate matter.     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Use of Stable Isotopes to Identify Sources of Mercury in Sediments: A Review and Uncertainty Analysis

Mass-dependent and mass-independent mercury isotope fractionation potentially generates unique source signatures that can be used to apportion contributions to sediment contamination. This article reviews findings from previous investigations that have used mercury isotopes to identify sources. It also discusses a mass balance mercury isotope fractionation model that simulates changes in isotopic source signatures in aquatic systems caused by natural biogeochemical cycling. According to the model, the extent of source signature alteration depends on chemical speciation, with more labile forms exhibiting greater isotopic fractionation. Apportionment is tractable when differences between δ²⁰²Hg of sources are larger than potential changes in isotopic signatures following the release of mercury into the environment.     

Evaluating anthropogenic N inputs to diverse lake basins: A case study of three Chinese lakes

The environmental degradation of lakes in China has become increasingly serious over the last 30 years and eutrophication resulting from enhanced nutrient inputs is considered a top threat. In this study, a quasi-mass balance method, net anthropogenic N inputs (NANI), was introduced to assess the human influence on N input into three typical Chinese lake basins. The resultant NANI exceeded 10 000 kg N km⁻² year⁻¹ for all three basins, and mineral fertilizers were generally the largest sources. However, rapid urbanization and shrinking agricultural production capability may significantly increase N inputs from food and feed imports. Higher percentages of NANI were observed to be exported at urban river outlets, suggesting the acceleration of NANI transfer to rivers by urbanization. Over the last decade, the N inputs have declined in the basins dominated by the fertilizer use but have increased in the basins dominated by the food and feed import. In the foreseeable future, urban areas may arise as new hotspots for nitrogen in China while fertilizer use may decline in importance in areas of high population density.

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